Electrolyte sheet with regions of different compositions and fuel cell device including such

• US 20080075984A1
• Filed: 09/27/2006
• Published: 03/27/2008
• Est. Priority Date: 09/27/2006
• Status: Active Grant

• Current Assignee: Corning Incorporated
• Original Assignee: Corning Incorporated
• Inventors: Ketcham, Thomas Dale, Garner, Sean Matthew, Badding, Michael Edward, St Julien, Dell Joseph, Hagg, Sandra Lee, Miller, Jeffrey Allen
• Granted Patent: US 7,820,332 B2
• Time in Patent Office: Days
• US Class Current: 429/12
• CPC Class Codes: H01M 2300/0077 based on zirconium oxide
• CPC Class Codes: H01M 2300/0088 Composites
• CPC Class Codes: H01M 8/1253 the electrolyte containing zirconium oxide
• CPC Class Codes: H01M 8/126 the electrolyte containing cerium oxide
• CPC Class Codes: H01M 8/2432 Grouping of unit cells of planar configuration
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

An electrolyte sheet comprising two major surfaces, the electrolyte sheet including regions of differing compositions, so that (i) at least one of these regions has at least 1.5 times higher ionic conductivity than at least one other region; (ii) wherein the at least one other region has 20% more tetragonal phase zirconia per volume than the least one region with higher ionic conductivity; and (iii) when viewed in cross-section taken through said major surfaces at least one of the regions exhibits a non-uniform thickness.

Claims

1. An electrolyte sheet comprising two major surfaces, said electrolyte sheet having regions of differing compositions, so that (i) at least one of said regions has at least 1.5 times higher ionic conductivity than at least one other region;

(ii) wherein said at least one other region has 20% more tetragonal phase zirconia per volume than said at least one region with higher ionic conductivity; and

(iii) when viewed in cross-section taken through said major surfaces at least one of said regions exhibits a non-uniform thickness.

2. The electrolyte sheet having regions of differing compositions according to claim 1, wherein (i) the at least one of said regions with higher ionic conductance includes a composition selected from at least one of:

zirconia 6-10 mole % yttria;

6-10 mole % ytterbia, lutetia, erbia, thulia;

zirconia doped with 7-12 mol % scandia; and

mixtures of zirconia 6-10 mole % yttria;

6-10 mole % ytterbia, lutetia, erbia, thulia;

zirconia doped with 7-12 mol % scandia; and

(ii) at least one other region has higher strength and includes a composition selected from at least one of;

zirconia 2-4 mole % yttria;

zirconia 2-4 mole % yttria or rare earth oxide (oxides of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu);

zirconia doped with 9-12 mole % ceria;

zirconia doped with 1.5-5 mole % yttria or rare earth oxide and 0.5-15 mole % yttrium, or rare earth niobate, or yttrium, or rare earth tanatalate (i.e. YNbO₄);

zirconia doped with 1.5-5 mole % yttrium or rare earth oxide and 0.5-15 m % rare earth, or magnesium or calcium, tungstate, yttrium or rare earth, or magnesium, or calcium molybdnate (CaWO₄);

or zirconia doped with 0.5-4 mole % yttria or rare earth oxide and 5-20 mole % TiO₂ or SnO₂ and mixtures there of.

3. The electrolyte sheet having regions of differing compositions according to claim 2, wherein said regions contain less than 10 volume percent alumina.

4. The electrolyte sheet according to claim 1, said electrolyte sheet having a plurality of regions of higher ionic conductivity and at least one region with lower ionic conductivity.

5. A solid oxide fuel cell device comprising:

(i) at plurality of anodes,

(ii) at plurality of cathodes;

(iii) a solid oxide electrolyte sheet of claim 4 disposed between said anodes and cathodes, such that said regions of higher ionic conductivity are sandwiched between said cathodes and said anodes.

6. The electrolyte sheet according to claim 4, wherein said plurality of regions with higher ionic conductivity include a composition selected from at least one of:

zirconia doped with 6-10 mole % yttria;

zirconia doped with 6-10 mole % ytterbia;

zirconia doped with 7-12 mole % scandia.

20. The electrolyte sheet according to claim 1 wherein said regions of different compositions correspond to different layers of the electrolyte sheet, and wherein said electrolyte sheet has a plurality of regions with a higher ionic conductivity than said at least one other region.

7. An electrolyte sheet comprising two major surfaces, said electrolyte sheet having regions of differing compositions, so that (i) at least one of said regions has at least 1.5×

higher ionic conductivity than at least one other region;

(ii) the least one other region has higher strength than said at least one of said regions with higher ionic conductivity, wherein said at least one other region with higher strength has 20% more tetragonal phase zirconia per volume than said at least one region with higher ionic conductivity; and

(iii) when viewed in cross-section taken through said major surfaces at least one of said regions exhibits a non-uniform thickness.

8. The electrolyte sheet having regions of differing compositions according to claim 7, wherein the at least one of said regions with higher ionic conductivity includes 8 mole % ytterbia.

9. The electrolyte sheet having regions of differing compositions according to claim 7, wherein the at least one of said regions with higher ionic conductivity includes a composition selected from at least one of:

zirconia doped with 6-10 mole % yttria;

zirconia doped with 6-10 mole % ytterbia;

zirconia doped with 7-12 mole % scandia.

10. The electrolyte sheet having regions of differing compositions according to claim 7, wherein the at least one at least one other region includes a composition selected from at least one of:

zirconia doped with 2 to 4 mole % yttria;

zirconia doped with 2-4 mole % rare earth oxide (oxides of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu);

zirconia doped with 9-12 mole % ceria, zirconia doped with 1.5-5 mole % yttria or rare earth oxide and 0.5-15 mole % of yttrium or rare earth niobate or rare earth tanatalate (i.e. YNbO₄), or zirconia doped with 0.5-4 mole % yttria or rare earth oxide; and

zirconia doped with 5-20 mole % TiO₂ or SnO₂ and mixtures there of.

11. The electrolyte sheet having regions of differing compositions according to claim 7, comprising at least 3 regions, the first region including scandia doped zirconia, the second region including ytterbia doped zirconia, the third region including yttria doped zirconia.

12. The electrolyte sheet having regions of differing compositions according to claim 7, wherein said electrolyte sheet is a zirconia based electrolyte sheet with at least two different areas having different levels of yttria.

13. A solid oxide fuel cell device comprising:

(i) at least one anode,

(ii) at least one cathode;

(iii) a solid oxide electrolyte sheet of claim 7 disposed between said anode and cathode.

14. The solid oxide fuel cell device of claim 13, wherein said electrolyte sheet has a plurality of regions with sad higher ionic conductivity and at least one region with lower ionic conductivity.

15. The electrical power-generating solid oxide fuel cell assembly comprising:

a) an enclosed interior formed at least in part by one or more compliant electrolyte sheets according to claim 7;

b) one or a plurality of anodes disposed within the enclosed interior and supported on an interior facing surface of the compliant solid oxide sheet;

c) one or a plurality of cathodes supported on an other surface of the compliant solid oxide sheet at locations generally opposite the anodes on the interior surface;

d) fuel delivery means for supplying a fuel gas to the enclosed interior; and

e) electrically conductive material connected to the anodes and cathodes for drawing electrical current from the assembly.

16. The electrical power-generating solid oxide fuel cell assembly according to claim 15 wherein said at least one other region of said electrolyte sheet with higher strength is situated adjacent to the perimeter of the electrolyte sheet, and wherein said plurality of anodes and cathodes are situated on opposing sides of said electrolyte regions of higher ionic conductivity.

17. The electrolyte sheet according to claim 7, wherein at least one of said major surfaces of said electrolyte sheet has regions of different compositions, some of said regions having higher ionic conductivity than said one at least one other region.

18. The electrolyte sheet according to claim 16, wherein said electrolyte sheet is substantially flat with the thickness variation of less than 3 μ

m.

19. The electrolyte sheet according to claim 17 wherein said at least one other region with higher strength is situated adjacent to the perimeter of the electrolyte sheet.

21. The electrolyte sheet according to claim 13 wherein said at least one other region with higher strength is situated adjacent to the perimeter of the electrolyte sheet.